Method for controlling bacteria and fungi



United States Patent 3,276,954 METHOD FOR CONTROLLING BACTERIA AND FUNGIFrancis X. OShea, Wolcott, Bogislavvon Schmeling, Hamden, and MitchellD. Dudarevitch, Cheshire, Conn., assignors to United States RubberCompany,

New York, N.Y., a corporation of New Jersey No Drawing. Filed June 9,1965, Ser. No. 462,732

18 Claims. (Cl. 167-.-30) M M This invention relates to fungicides andbactericides, more particularly to agricultural and industrialmicrobicides.

The chemicals of the present invention which show such biocidal activitymay be represented by the general formula wherein R is an alkyl radicalof up to 12 carbon atoms or a cycloalkyl radical of to 8 carbon atoms oran aralkyl radical of 7 to 9 carbon atoms, R; and R are hydrogen ormethyl, and R and R are alkyl radicals having up to 5 carbon atoms eachor are radicals in which R and R .are joined to form with the nitrogenatom a radicals'elected from the group consisting of morpholinyl, pyrrolidinyl and piperidinyl radicals. t

The compounds of the present invention and their preparation aredisclosed and claimed as new chemicals in the copending applicationSerial No. 462,745, filed June 9, 1965 of Francis X. OShea. Thecompounds are prepared by reacting one molar equivalent of a phenolicompound of the formula wherein R, R and R are as above described, withtwo molar equivalents of formaldehyde, two molar equivalents of asecondary amine of the formula R R NH in' which R and R are as abovedescribed and one molar equivalent of carbon disulfide in an alcoholsolvent. The

overall equation for the reaction is:

The hydrocarbon substituted phenols which may be used include o-cresol,

o-ethylphenol, o-isopropylphenol, o-t-butylphenol, o-t-amylphenol,

o- (alpha-methylpentyl) phenol, o-(alpha-methylheptyl)phenol,

Patented Oct. 4, 1966 o-( alpha-methylnonyl phenol,

oalpha-methylundecyl) phenol, o-cyclohexylphenol,

o- (methylcyclohexyl phenol, o-cyclooctylphenol,

o-benzylphenol,

oalpha-methylbenzyl) phenol,

o- (alpha,alpha-d imethylbenzyl phenol,

2,3 -dimethylphenol,

2,5 -dimethylphenol,

2,3 ,5 -trimethy1phenol,

6-isopropyl-m-cresol,

2-isopropyl-3 ,5 -dimethylpheno1, 6-t-butyl-m-cresol,

2-t-butyl-3 ,5 -dimcthylphenol, 6-sec-.butyl-rn-cresol,

2-se c-butyl3 ,5 -dimethy1phenol,

6- (-alpha-methylpentyl) -m-cresol,

2- alpha-methylpentyl) -3 ,5 -dimethylpheno1, G-t-amyI-m-cresol,

2-t-amyl-3 ,5 dimethylphenol, 6-(alpha-methylheptyl) m-cresol, 2-(alpha-methylheptyl) -3 ,5 -dim'ethylphenol, 6( alpha-methylnonyl)-m-cresol,

2- alpha-methyln onyl) -3 ,5 -dimethy1phenol, 6- alpha-methylundecyl-m-cresol,

2- (alpha-methylun-decyl) -3 ,5 -dimethylphenol, 6-t-o ctyl-m-cresol,

2-t-octyl-3 ,5 -dimethylpheno1, 6-cycloheXyl-m-cre-sol,

' 2-cyclohexyl-3,S-dimethylphenol,

6-'cycl0octyl-m-cresol, 2-cyclooctyl-3,S-dimethylphenol,fi-benzyl-m-cresol, 2-benzyl-3,S-dimethylphenol,

6( alpha-methylbenzyl) -m-cresol, 2-(alpha-methylbenzy1)-3,5-xy1enol;The preferred phenols are o-alkylphenols in which the. alkyl groupcontains from onerto four carbon atoms such as o-cresol ando-t-butylphenol. ,The secondary amines which may be used includedimethylamine, methylethylamine, diethylamine, dibutylamine,diamylamine, morpholine, pyrrolidine and piperidine. The preferred amineis dimethylamine.

The following chemicals are illustrative of the compounds of the presentinvention using the above referred hydrocarbon substituted phenols andsecondary amines in their preparation:

3-methyl-4-hydroxy-5-(dimethylaminomethyhbenzylN,N-dimethyldithiocarbamate3-t-butyl-4-hydroxy-5-(dimethylaminomethyl)benzy1N,Ndimethyldithiocarbamate 3cyclohexyl-4-hydroxy-5-(dimethylaminomethyl)benzylN,N-dimethydithiocarbamate 3cyclooctyl-4-hydroxy-5-(dimethylaminomethyl)benzylN,N-dimethyldithiocarbarnate3-isopropyl-4-hydroxy-5-(dimethylaminomethyl)benzy1 IN,N-dimethyldithiocarbamate Y 3-sec-butyl-4-hydroxy-5-(dimethylaminomethyl benzyl N,N-dimethyldithiocarbamate3-(alphaqnethylnonyl)-4-hydroxy-5-(dimethylaminomethyhbenzylN,N-dimethyldithiocarbamate2,5dimethyl-3-(dimethylaminomethyl)-4-hydroxybenzylN,N-dimethyldithiocarbamate2,3-dimethyl-4-hyd-roxy-5-(dimethylaminomethyl)benzylN,N-dimcthyldithiocarbamate3-methyl-4-hydroxy-5-(dibutylaminomethyl)benzylN,N-dibutyldithiocarbamate3-methyl-4-hydroxy-5-(ethylisopropylaminomethyl)- benzylN-ethyl-N-isopropyldithiocarbamate3-methyl-4-ahydroxy-5-[di(betaahydroxyethyl) aminometh- 3 yl]-benzylN,N-di(beta-hydroxyethyl)dithiocarbamate 2-t-butyl-4-(morpholinothiocarbonylthiomethyl)-6- (morpholinomethyl) phenol2-t-buty1-4- (piperidinothiocarb onylthiomethyl) -6-(piperidinomethyl)phenol2-methyl-4-(morpholinothiocarbonylthiomethyl)-6-(morpholinomethyl)phenol2-Inetl1yl-4-(piperidinothiocarbonylthiomethyl)-6- I (piperidinomethyl)phenol v 2,6-dimethyl-3-(alpha,alpha-dimethylbenzyl)-4-hydroxy5-(dimethylaminomethyl)benzyl N,N-dimethyldithiocarbamate f2,64iimethyl-3 alpha-methylundecyl) -4-hydroxy-5-(dimethylaminomethyDbenzyl N,N-dimethyldithiocarbamate The followingExamples 1 to 11 illustrate the preparation of the present compounds.Examples 12 to 15 illustrate the effectiveness of the compounds asfungicides and bactericides according to the present invention. Allparts and percentages referred to herein are by weight.

EXAMPLE 1 The preparation of 3-methyl-4-hydroxy-5-(dimethylaminomethyl)benzyl N,N-dimethyldithiocarbamate To a solution of 5 4 g. (0.5 mole) ofo-cresol and 190 g. (1.05 moles) of 25% dimethylamine in 250 ml. ofethanol was added 84 g. (1.05 moles) of 37% aqueous formaldehydedropwise with cooling to keep the temperature below 30 C. To thesolution was then added 38 g. (0.5 mole) of carbon disulfide and thesolution was heated under reflux for three hours. The solution was thencooled and poured into water.. The product which separated was extractedwith ether.

The ether solution was shaken with a solution of 50 ml. of concentratedHCl in 200 ml. of water. The ether layer from this extraction yielded asolid precipitate which was filtered oif, washed with hexane and dried,wt.=15 g. This is the by-product2-methyl-4,6-bis(dimethylthiocarbamylthiomethyDphenOl, M.P..123-125 C.

The aqueous layer from the extraction was neutralizedwith aqueous sodiumbicarbonate. The solid precipitate which formed was extracted with anether-benzene mixture, dried with anyhydrous sodium sulfate andevaporated down to a solid residue of 3-methy1-4-hydroxy-5-(dimethylaminomethyl)benzyl N,N dimethyldithiocarbamate weighing 92 g.(62%), M.P. 9899 C. after recrystallization from methanol. 7

I. Anal.Calcd for C HQ N OS C, 56.4%; H, 7.39%; N, 9.39%; S, 21.45%.Found: C, 56.3%; H, 7.48%; N, 9.40%;8, 21.23%.

EXAMPLE 2 The preparation of 3-t-bulyl-4-hydroxy-5-(dimethylaminomethyl)benzyl N,N-dirnethyldithiocarbamate T he preparation of3-isopropyl-4-hydroxy-5- (dimethyl- 'amz'nomethyl) benzylN,N-dimethyldithiocarbamate Using the method described in Example 1,o-isopropyl-. phenol, was converted to3-isopropyl-4-hydroxy-5-(dimethylaminomethyl)benzyl N,Ndimethyldithiocarbamate in 57% yield, M.P. 79-80" C. afterrecrystallization from ethanol.

Anal.-Calcd for C H N OS N, 8.59%; S, 19.62%.

Found: N, 8.5%; S, 19.62%.

EXAMPLE 4 The preparation of 3-sec-butyl-4-hydroxy-5-(dimethyhaminomethyl) benzyl N,N-dimethyldithiacarbamate Using the methoddescribed in Example 1, o-sec-butylphenol was converted to3-sec-butyl-4-hydroxy-5-(dimethylaminomethyl)benzylN,N-dimethyldithiocarbamate in 50% yield, M.P. 90-91" C. afterrecrystallization from ethanol.

Anal.Calcd for C HggNgOSzZ N, 8.24%; S, 18.80%. Found: N, 8.20%; S,19.11%.

EXAMPLE 5 The preparation of 3-(alpha-methylnonyl)-4-hydroxy-5-(dimethylaminomethyl) benzyl N,N dimethyldithiocarbamate Using themethod described in Example 1, o-(alphamethylnonyl)phenol was convertedto 3-(alpha-methylnonyl): 4 hydroxy-S-(dimethylaminomethyl) phenol in72% yield. The product was a viscous oil.

EXAMPLE 6 The preparation of2,5-dimethyl-3-(dimethylaminomethyl)-4-hydroxybenzylN,N-dimethyldithiocarbamate To a solution of 122 g. (1 mole) of2,5-dimethylphenol and 360 g. (2 moles) of 25% dimethylamine in 200 ml.of ethanol was added 162 g. (2 moles) of 37% aqueous formaldehydedropwise with cooling to keep the temperature below 30 C. Carbondisulfide -(77 g., 1 mole) was then added and the reaction mixture washeated under reflux for four hours. It was then poured into water andthe precipitate which formed was filtered ofland washed with ethanol.The yield of 2,5-dimethyl-3-(dimethylaminomethyl)-4-hydroxybenzylN,N-dimethyldithiocarbamate was 272 g., 91%, M.P. 143-145 C. afterrecrystallization from ethanol.

EXAMPLE 7 The preparation of2,3-dimethyl-4-hydroxyy5-(aimethylaminomethyl) benzylN,N-dimethyldithiocarbamale Using the method described in Example 1,2,3-dimetl1-' ylphenol was converted to2,3-dimethyl-4-hydroxy-5-(dimethylaminomethyl)benzylN,N-dimethyldithiocarbamate in 91% yield, M.P. 90-91 C. afterrecrystallization from methanol.

EXAMPLE, 8

The preparation of 2-t-butyl-4-(morpholinothiocarbonyl- 'thiomethyl) -6-(morpholinomethyl) phenol To' a solution of 75 g. (0.5 mole) ofo-t-butylphenol and 87 g. (1 mole) of morpholine in 400 ml. of ethanolwas added 84 g. 1.05 moles) of 37% aq. formaldehyde with cooling to keepthe temperature below 30 C. The solutionwas stirred at room temperaturefor 1% hours and then was heated at reflux for 2 /2 hours. Thesolution'was cooled to 50 C. Carbon disulfide (53 g., 0.7 mole) was thenadded and the solution was heated at reflux for one hour.

The reaction mixture was diluted with water and the product whichseparated was extracted with ether. 'The ether layer was then shakenwith dilute hydrochloric acid and the acidic ext-ractwas separated andneutralized with aqueous sodium carbonate- The product which separatedwas extracted with ether, washed with Water, dried over anhyd. sodiumsulfate and evaporated down to yield 115 g. (55%) of2-t-butyl-4-(morpholinothiocarbonylthio--methyl)-6-(morpholinomethyDphenol, M.P. 71-73 C. after recrystallizationfrom hexane.

EXAMPLE 9 The preparation of 2-t-butyl-4-(piperidinothiocarbonyladded 84g. 1.05 moles) of 37% aq. formaldehydewith cooling to keep thetemperature below 30 C. The solution was stirred at room temperature forone hour and then was heated at reflux for 3 hours. The solution wasthen cooled to 50 C. Carbon disulfide (53 g., 0.7 mole) was then addedand the solution was heated at reflux for two hours.

The reaction mixture was diluted with water and the product whichseparated was extracted with ether. The

ether layer was then shaken with dilute hydrochloric acid and the acidicextract was separated and neutralized with aqueous sodium carbonate. Theproduct which separated was extracted with ether, washed with water,dried over anhyd. sodium sulfate and evaporated down to yield 122 g.(58%) of2-t-butyl-4-(piperidinothiocarbonylthiomethyl)-6-piperidinomethyl)phenol,M.P. 9495 C. after recrystallization from acetone.

EXAMPLE 10 The preparation of3-cyclohexyl-4-hydroxy-5-(dimethylaminomethyl)benzylN,N-dimethyldithiocarbamate To a solution of 88 g. (0.5 mole) ofo-cyclohexylphenol and 190 g. (1.05 moles) of 25% aq. dimethylamine in500 ml. of ethanol was added 84 g. (1.05 moles) of 37 aq. formaldehydewith cooling to keep the temperature below 30 C. Thesolution was stirredat room temperature for one hour and then was heated at reflux for twohours. The solution was cooled, carbon disulfide (53 g., 0.7 mole) wasadded, and the solution was heated at reflux for two hours.

The reaction mixture was diluted with water and the product wasextracted with benzene. The benzene layer was filtered to remove someinsoluble material. It was then shaken with dilute hydrochloric acid andthe acidic extract was separated and neutralized with aqueous sodiumcarbonate. The product which separated was extracted with benzene,washed with water, dried over anhyd. sodium sulfate and evaporated down.to yield 127 g. (74%) of 3-cyclohexyl-4-hydroxyS-(dimethylaminomethyl)benzyl, N,N-dimethyldithiocarbamate, M.P. 98- 100C. after recrystallization from hexane.

EXAMPLE 1 1 The preparation of 3-cycl0octyl-4-hydroxy-5-(dimethylaminomethyl) benzyl N,N-dimethyldithiocarbamate To a solution of 62 g.(0.19 mole) of ocyclooctylphenol and 68.4 -g. (0.38 mole) of 25% aq.dimethylamine in 200 ml. of ethanol was added 30.8 g. (0.38 mole) of 37%aqueous formaldehyde with cooling to keep the temperature below 30 C.Carbon disulfide (14.4 g., 0.19 mole) was added and the solution washeated at reflux for five hours.

The reaction mixture was diluted with water and the product wasextracted with ether. The ether layer was then shaken with dilutehydrochloric acid and the acidic extract was separated and neutralizedwith aqueous sodium carbonate. The product which separated was extractedwith ether, washed with water, dried over anhyd. sodium sulfate andevaporated down to yield 3-cyclooctyl- 4-hydroxy-5(dimethylamiuomethyl)benzyl N,N-dimethyldithiocarbamate as a liquidresidue.

EXAMPLE 12 This example demonstrates the eflectiveness of the chemicalsof this invention as agriculturall protective fungicides as testedagainst Alternaria solam', the causal organism of tomato early blight.

Sixteen hundredths (0.16) gram of the chemical to be tested wasdissolved in twenty ml. of acetone and mg. of a non-ionic surface-activeagent (a condensation product of an alkyl phenol and ethylene oxide).The acetone and surface-active agent are known to be inactive in thebiological tests run. The mixture was diluted serially with distilledwater, giving in some cases suspensions containing 500 to 2000 parts permillion (p.p.m.) and in other cases 50, 200 and 800 p.p.m. of thechemical. These suspensions were sprayed on duplicate six inch tomatoplants (variety Clarks Early Special) using a gun-type were then placedin the greenhouse, together with untreated check plants. Twenty-fourhours later the treated and untreated check plants were inoculated witha suspension of Alternaria solani spores by means of a 20 second sprayfrom an atomizer sprayer (delivery rate 1 ml. per second). The plantswere then kept overnight in a control chamber at a temperature of 75 F.and 100% relative humidity. In the morning the plants were transferredto the greenhouse. Three days later the disease was scored by comparingthe number of disease lesions of the treated plants with the untreatedcheck.

The formula to determine percent control is:

Ave. No. lesions on treated plant Ave. N0. lesions on untreated plant=Percent control The results of the tests are shown in the followingtable:

Percent Disease Control Percent Disease Control 500 p.p.m. 2,000 p.p.m.

3-methyl-4-hydroxy-5-(dibutylaminomethyl) benzyl N,N-dibutyldithiocarbaruate3-methyl-thydroxy-5-(ethylisopropylaminomethyDbenzylN-ethyl-N-isopropyldithiocarba'mato 3-methyl-4-hydroxy-5ldi(beta-hydroxyethyl) aminornethyflbenzyl N,N-di(beta-hydroxyethyDdithiocarbaruate 2,5-dimethyl-3-(dimethylaminomethyD-4- hydroxybenzyl N,N-dimethyldithiocarbamate2,3-dimethyl-4-hydroxy-5-(dimethylarninomethyDbenzylN,N-dimethyldithiocarbama e2-t-butyl-4-(morpholinothiocarbonylthiornethyl)-6-(morpholinomethyl)phenol2-t-butyl-4-(piperidinothiocarbonylthio methyl)-6-(piperidinomethyl)phenol EXAMPLE 13 This example demonstrates the effectiveness of thechemicals of this invention as bactericides as tested by the agar platetechnique.

Thirty-five mg. of 3-methyl-4-hydroxy-5-(dimethylaminome'thyDbenzylN,N-dimethyldithiocarbamate was dissolved in 5 ml. of acetone to whichwas added 45 ml. of a 0.01% aqueous solution of a non-ionicsurfaceactive wetting agent (isooctyl phenyl polyethoxy ethanol). Threeml. of this chemical preparation was pipetted into a 50 ml. Erlenmeyerflask containing 5 ml. nutrient medium and kept liquified'in a waterbath at 47 C. The bacterial inoculum consisting of a spore suspension ofPseudomonas aeruginosa was then added to this preparation at the amountof 0.25 ml. per flask. Thus the flask contained a chemical concentrationof 255 p.p.m. The preparation was then poured into 2 /2" Petri platesand incubated at 30 C. Similar tests were made at a con centration ofthe chemical of 128 p.p.m. The results were taken 24 hours later byexamining the plates for bacterial growth with a bacterial colonycounter and comparing the chemical treatment with an untreated,inoculated check.

The untreated, inoculated (check) test showed severe bacterial growth,whereas the test with the3-methyl-4-hydroxy-S-(dimethylaminomethyl)benzyl N,Ndimethyldithiocarbamate showed no bacterial growth at 128 ppm. or 255p.p.m. of the chemical.

EXAMPLE 14 taining three drops per liter of a non-ionic surface-activeagent (isooctyl phenyl polyethoxy ethanol). Aliquots were removed fromthis stock solution (usually containing 1000 or 100 ppm. of chemical) tosterile, screwcapped, clear one ounce bottles suflicient to obtain afinal concentration of 1, 5, 50 and 100 p.p.m. To each bottle was addedsulfate reducing broth inoculated with Desulfovibrz'o desulfuricans(1.5%). The recipe for the sulfate reduction broth was as follows:

Sodium lactate, U.S.P 4.0 m1. Yeast extract 1.0 gm. Ascorbic acid 0.1gm. 0.2 gm. K HPO (anhydrous) 0.01 gm. Fe(SO (NH4)z6H2O gm. Sodiumchloride 10.0 gms. Distilled water 1000.0 mls. pH adjusted to 7.5.

The caps were replaced and the bottles incubated at.32- 35 C. with dailyobservations for one week and weekly observations thereafter for a totalof 4 weeks incubation.

The results of the test are shown in the following table:

Concentration (in p.p.m.) Compound3-methyl-4-hydroxy-5-(dimethylaminomethybbenzyl N,N-dimethyldithiocarbanrate 3-t-butyl-4-hydroxy5-(dnnethylaminomethyDbenzylN,N- dimethyldithiocarbamate3-cyclohexyl-4-hydroxy-5-(drmethylaminomethyl) benz N,dimethyldithiocarbamate3-cyclooctyl4-hydroxy-5-(drmethylaminomethyDbenzyl N,N-dimetuyldithiocarbamate3-isopropyl-4hydroxy-5-(drmethylamiuomethyDbenzyl N,N-dimethyldithiocarbamate3-sec-butyl-4-hydroxy-5(drmethylaminomethyl)benzy1 N,N-dimethyldithiocarbamate 3-methyl-4 hydroxy-5-(ethylisopropyl-.aminoruethyDbenzyl N-ethyl-N- isopropyldithiocarb amate T2,Erdimethyl-3-(dimethylammomethyl) -4-hydroxybenzyl N ,N-dimethyldithiocarbamate2,3-dimethyl-4-hydroxy-5-(dimethylaminomethyDbenzyl N,N-dimethyldithiocarbamate2-t-butyI-4-(piperidinothrocarbonylthiomethyl)-6-(piperidrnon1ethyl)-phenol Growth and Media Blackening. '-=N Growth or Blackenrng.

8 EXAMPLE 15 This example demonstrates the etfectiveness of thechemicals of the invention as material preservatives against the variousdegradative bacteria andfungi causing deterioration of textiles, paper,wood, etc.

Samples of ten ounce cot-ton duck (70 lbs. breaking strength) weretreated with acetone solutions of the chemicals and dried at 60-65 C.for 15 minutes, giving a deposition of 1% of the chemical on thefibers-Generally 0.1% to 10%, of the chemical based on the weight of thematerial being treated will .be used in practice. Samples were thentested according to FederalSrpec'ification CCC-T-191b, Textile TestMethods, Method 5762, Soil Burial Method. The test was carried out asfollows: Strips, 2 x 6 inches of the .thu's treated fabric and str-ipsofuntreated control fabric were buried vertically by inserting thematerial into test soil to a depth of 5 inches. The soil wasmicrobiologically active, had a pH of about 6.5, a moisture content ofabout 25%, and contained microorganisms such as Triclzoderma lignorwn,Myrothecium verrucaria, Alternania solani, Chaetonium globosum, Fusariummoniliforme, Aspergillus ustus, Penecillium spp.

The soil beds were maintained at 2832' C. and relative humidity. After14 daysburial, the specimens were removed, gently washed and dried. Someof the strips were leached by 24' hours immersion withsix hand changesin water. The breaking strengths of the treated and untreated controlstrips were determined for comparison of loss of breaking strength ofthe treated fabric with the untreated control.

yl groups.

Loss in Breakin Strength (in lbs. Compound Uuleached Leeched3-methyl-4-hydroxy-5-(dimethylaminomethyl) benzylN,N-dimethyldithiocarham am 5 503-t-butyl-4-hydroxy-5-(dimethylaminomethyl) beuzylN,N-dimethyldithiocarbarn are 52 Q Untreated control 73 73 wherein R isalkyl of 1 to 12 carbon atoms,"cycloa1ky 1 of 5 to 8 carbon atoms oraralkyl of 7 to 9 carbon atoms, R l

and R are hydrogen or methyl, R and R are alkyl having 1 to 5 carbonatoms eachor are joined to form with the nitrogen atom morpholinyl,pyrrolidinyl or piperidin- 9 2. The method of controlling bacteria andfungi which comprises contacting bacteria and fungi with a compoundhaving the formula R CHzNRaRA s omsi l Nn m wherein R is alkyl of 1 to12 carbon atoms, cycloalkyl of to 8 carbon atoms or aralkyl of 7 to 9carbon atoms, R and R are hydrogen or methyl, R and R are alkyl having 1to 5 carbon atoms each or are joined to form with the nitrogen atommorpholinyl, pyrrolidiny-l or piperidinyl groups.

3. The method of controlling bacteria and fungi which comprises applyingto loci subject to attack by bacteria and fungi a compound having theformula wherein R is alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 8canbon atoms or aralkyl of 7 to 9 carbon atoms, R and R are hydrogen ormethyl, R and R are alkyl having 1 to 5 carbon atoms each, or are joinedto form with the nitrogen atom morpholinyl, pyrrolidinyl or piperidinylgroups.

4. The method of controlling fungi on plants which comprises contactingplants with a compound having the formula wherein R is alkyl of 1 to 12carbon atoms, cycloalkyl of 5 to 8 carbon atoms or aralkyl of 7 to 9carbon atoms, R and R are hydrogen or methyl, R and R are alkyl having 1to 5 carbon atoms each or are joined to form with the nitrogen atommonpholinyl, pyrrolidinyl or piperidinyl groups.

5. The method of protecting material capable of nourishing bacteria andfungi from destruction by such pests which comprises bringing thematerial into contact with a compound having the formula R1 RI wherein Ris alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 8 carbon atoms oraralkyl of 7 to 9 carbon atoms, R and R are hydrogen or methyl, R and Rare alkyl having 1 to 5 carbon atoms each or are joined to form with thenitrogen atom morpholinyl, pyrrolidinyl or piperidinyl groups.

10 6. Material normally subject to microbiological decomposition butmade resistant to such decomposition by having incorporated therein acompound having the formula wherein R is alkyl of 1 to 12 carbon atoms,cycloalkyl of 5 to 8 canbon atoms or aralkyl of 7 to 9 carbon atoms, Rand R are hydrogen or methyl, R and R are alkyl having 1 to 5 carbonatoms each or are joined to form with the nitrogen atom morpholinyl,pyrrolid'inyl or piperidinyl groups.

7. Oellulosic material impregnated with a compound having the formula RCHRNRQR wherein R is alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 8carbon atoms or aralkyl of 7 to 9 carbon atoms, R and R are hydrogen ormethyl, R and R are alkyl having 1 to 5 carbon atoms each or are joinedto form with the nitrogen atom morpholinyl, pyrrolidinyl or piperidinylgroups.

8. Fabric having incorporated therein a compound having the formula RCH2NRa 4 wherein R is alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to8 carbon atoms or aralkyl of 7 to 9 carbon atoms, R and R are hydrogenor methyl, R and R are alkyl having 1 to 5 carbon atoms each or arejoined to form with the nitrogen atom morpholinyl, pyrrolidinyl or piperidinyl groups.

9. The method of controlling microorganisms which comprises applying3-methyl-4-hydroxy-5-(dimethylaminomethyl)benzylN,N-dimethyldithiocarbamate to a me dium which normally supports thegrowth of microorganisms.

10. The method of controlling microorganisms which comprises applying3-t-butyl-4-hydroxy-5-(dimethylaminomethyDbenzylN,N-dimethyldithiocarbamate to a medium which normally supports thegrowth of microorganisms.

11. The method of controlling microorganisms which comprises applying3-cycloocty1-4-hydroxy-5-(dimethylaminomethyDbenzyl.N,N-dimethyldithiocarbamate to a medium which normally supports thegrowth of microorganisms.

12. The method of controlling microorganisms which comprises applying2,-3-dimethyl-4-hydroxy-5-(dimethylaminomethylybenzylN,N-dimethyldithiocarbamate to a medium which normally supports thegrowth of microorganisms.

13. The method of controlling microorganisms which comprises applying2,5-dimethy1 3 (dimethylaminomethyl)-4-hydroxybenzylN,N-dimethyldithiocanbamate to a medium which normally supports thegrowth of microorganisms.

14. The method of controlling fungi on plants which comprises applying3-methyl 4 hydroxy-S-(dimethylaminomethyhbenzylN,N-dimethy1dithiocanbamate to plants.

15.The method of controlling fungi on plants which lCOlIlPI'iSCSapplying 3-t-butyl-4-hydroxy-5-(dimethylaminomethyl)benzylN,N-dimethyldithiocarbamate to plants.

16. The method of controlling fungi on plants which comprises applying3-cyclooctyl-4-hydroxy-5(dimethylaminomethyl)benzylN,N-dimethyldithiocarbamate to plants.

17. The method of controlling fungi on plants .which .12. comprisesapplying 2,3-dimethyl-4-hydroxy-5-(dimethylaminomethyDbenzyl'N,N-dimethyldithiocanbama-te to plants.

18. The method of controlling fungi, on plants which comprises applying2,5-dimethy1 3 (dimethylaminomethyl)-4-hydroxybenzylN,N-dimethyldithiocarbamate to plants.

No references cited..

JULIAN S. LEV-HT, Primary Examiner.

STANLEY I. FRIEDMAN, Assistant Examiner.

1. THE METHOD OF CONTROLLING MICROORGANISMS WHICH COMPRISES APPLYING TOAMEDIUM WICH NORMALLY SUPPORTS THE GROWTH OF MICROORGANISMS A COMPOUNDHAVING THE FORMULA